Insights into the Chemistry of Transient <i>P</i>‐Chlorophosphanyl Complexes

CP or CP? One-electron oxidation of Li/Cl phosphinidenoid complexes led to the discovery of transient P-chlorophosphanyl complexes 1. Subsequent cross-coupling and rearrangement or elimination reactions yielded 2 and 3; the latter is the first structurally characterized phosphaquinomethane complex. ESR spectroscopy and DFT calculations support the existence of short-lived P-centered radicals.